Ketone acetals and orthoesters



United States Patent M 3,419,580 KETONE ACETALS AND ORTHOESTERS WilliamC. Kuryla, St. Albans, W. Va., assignor to Union Carbide Corporation, acorporation of New York No Drawing. Continuation-impart of applicationSer. No.

292,478, July 2, 1963. This application Apr. 2, 1965,

Ser. No. 450,178

11 Claims. (Cl. 260347.8)

This invention relates to novel ketene acetals and orthoesters and anovel process for the preparation thereof.

This application is a continuation-in-part of application Ser. No.292,478 now abandoned, filed July 2, 1963 in the name of the sameinventor as on the instant application.

Ketene acetals and orthoesters have heretofore been prepared by avariety of methods. Ketene acetals have been produced bydihydrohalogenation of a haloacetal with potassium-t-butoxide intertiary butanol, and by the reaction of an u-bromoorthoester withmetallic sodium. Orthoesters have been obtained by the alcoholysis of anaminoester hydrochloride obtained from the reaction of alcoholichydrogen chloride.

It has new been found that a new class of ketene acetals and orthoestersmay be synthesized by a novel process by the slow addition of adihaloalkene to a basic hydroxy compound, such as an alkali metalalcoholate having an electron donating atom in the position beta orgamma to the alcoholate oxygen atom.

In accordance with this novel process there are produced novel keteneacetals and orthoesters represented by the general Formula I:

lOiliIi X R.) a 1'2 Ltd...

wherein n is an integer of from 2 to 3, wherein m is zero or 1, andwherein A, depending upon the value of n, represents a radical selectedfrom the group consisting of tertiary radicals of the formula andsecondary radicals of the formula wherein R is alkyl or chloroalkyl andR is alkylidene or chloroalkylidene. The novel compounds of thisinvention may be accordingly represented by the ketene acetals of thefollowing Formula II and orthoesters of the Formula III (II) R R R a=caatialm II L112? im 2 (III) 3,419,580 Patented Dec. 31, 1968 saturateddivalent chain which forms a heterocyclic ring containing X as aheterocyclic atom; and wherein R represents alkyl, aryl, alkaryl,aralkyl, alkoxyalkyl or polyalkoxyalkyl and when taken with any Rrepresents a saturated divalent chain which forms a heterocyclic ringcontaining X as a heterocyclic atom. Accordingly, when R is selected inthis manner, together with an R substituent, there may be formed aheterocyclic ring containing up to 2, preferably 1 aza or oxaheterocyclic atom. Such heterocycles which may be formed includetetrahydrofuryl, pyrrolidenyl, oxalanyl, imidazolidenyl,tetrahydropyranyl, dioxamyl, piperidyl, piperazanyl, morpholinyl and thelike. Preferably said heterocyclic ring contains 5 or 6 members. Itishighly preferred that R and R when selected together in this manner forman alkylene chain and thus result in the formation of a monoheterocyclicring of 5 to 6 members. The said chain obtained formed by a combinationof R and R in this manner may be branched so as to result in theformation of an alkyl substituted heterocycle, said substituentscontaining up to about 4 carbon atoms. Suitable substituents above arealkyl groups of from about 1 to 8 carbon atoms and monocyclic andbicyclic hydrocarbon aryl, alkaryl, and aralkyl groups containing 6 to12 carbon atoms, such as phenyl, benzyl, tolyl, ethylbenzyl, naphthyland the like.

Eminently preferred for R are polyoxyalkylene radicals having from 2 to4 carbon atoms in each alkylene unit capped with an alkyl group such asthe monoalkyl etheric radicals of polyoxyethylene glycol,polyoxypropylene glycol, polyoxybutylene glycol, and po1y[mixedoxyethyleneoxypropylene] glycol and the like.

It is pointed out that the above structural formulae are deemed toinclude mixed ketene acetals and mixed orthoesters wherein thesubstituents on the radical generically designated A in Formula I aredissimilar.

In a first preferred embodiment the novel compounds of this inventionare derived from polyalkyleneoxy alcohols. The novel ketene acetals, inaccordance with this embodiment may be characterized by the formula:

R -0- lk le 0-11 a y and the orthoesters, by the formula:

RC [(O-alkylene)n O--R4]2 wherein R and R are as hereinbefore defined,wherein the alkylene group is a 1,2-alkylene group or a 1,3- alkylenegroup, and preferably contains from 2 to 4 carbon atoms such asethylene, 1,2-propylene, 1,3-propylene, 2,3-butylene, 1,2-butylene or1,3-butylene, wherein R is alkyl or aryl as hereinbefore set forth,preferably alkyl of from 1 to 6 carbon atoms, and wherein n is aninteger of at least one designating the number of repeating alkyleneoxygroups. It is pointed out that the alkyleneoxy chain may beheterogeneous, e.g., may be made up of mixed ethyleneoxy andpropyleneoxy groups containing from 1 to '25 preferably 1 to 10alkyleneoxy groups.

The novel compounds of this invention include ketene acetals andhaloketene acetals including mixed ketene acetals wherein the twoetheric moieties are dissimilar. Included among the novel ketene acetalsof this invention are the ketene and haloketene acetals, includingketene di(2-methoxyethyl) acetal,

ketene di(3ethoxypropyl) acetal,

methylketene di(2sec-butoxypropyl) chloroethylketenedi(3-isopropoxypropyl) acetal, bromoketene di(2-methoxybut-3-yl) acetal,chloroethyl(3-ethoxybutyl) acetal, chloromethylketenedi(3-n-hexoXy-propyl) acetal,

propylketene di(2-phenoxyethyl) acetal, isopropylketenedi(2-benzyloxyethyl) acetal, chloroethylketene di(3-[p-methylphenyl]propyl) acetal, ketene di(2-(N,N-dimethylaminoethyl)) acetal,di(3-(N-ethylaminopropyl)) acetal,

methylketene di(3-tetrahydrofurfuryl) acetal, methylketenedi(2-tetrahydrofurfuryl) acetal, methylketene di(3-tetrahydrofuryloxy)acetal, methylketene-di(2-pyrrolidinylmethyl) acetal, isopropylketenedi(3-pyrrolidinyl) acetal, butylketene di(4[ 1,2-oxazolidinylmethyl])acetal, ethylketene di(4-[ 1,3-OXO'13I1Y1H16thYll] )acetal, hexylketenedi 4-ethyl-3 -piperidinyl) acetal, bromoketene di(3-piperidinylmethyl)acetal, methylketene di (2- [N-ethylpiperidinylmethyl] )acetal, ketenedi(2-morpholinyl) acetal,

ethylketene di(N-piperizinylethyl) acetal,

as well as mixed ketene acetals which may be made by using a mixedalcoholate feed as will be obvious hereinafter, such as methylketeneZ-methoxyethyl, 3-methoxypropyl acetal and the like; the polyoxyalkyleneketene acetals such as ethylketene di(ethoxypoly-l,3-propoxy) acetal,methylketene di-(methoxypoly-l,2-ethoxy) acetal, methylketene di(butoxypoly-2,3-butoxy) acetal, chloroketene (butoxypoly[mixed-l,2-ethoXy-1,2-propoxy]) acetal, and the like.

The novel orthoesters which may be produced by the process of thisinvention include tri(2-methoxyethyl) orthoacetate, tri(2-methoxyethyl)orthopropionate, tri(2- ethoxy-2,3-butyl) orthochloroacetate,tri(3-ethoxypropyl) orthobutyrate, tri(3-phenylmethoxypropyl)orthoacetate, tri(2-isopropoxypropyl) orthopropionate, tri(2-ethoxy-2-phenylethyl) orthoacetate, tri(3-phenoxybutyl) orthoacetate,tri[2-(p-tolyloxy)] orthoacetate, tri(2-hexoxyethyl) orthobromoacetate,the orthoacetates and chloroorthoacetates of dipropylene glycolmonomethyl ether, the orthopropionates and orthobromopropionates oftriethylene glycol monomethyl ether, the orthoacetates andorthochloroacetates of methoxy polyethylene glycol, ethoxy polyethyleneglycol, and butoxy poly-1,2-propylene glycol, and butoxypoly-1,3-propylene glycol, the orthopropionates, orthochloropropionates,and orthobromobutyrates of methoxy polyethylene glycol, ethoxypolyethylene glycol, butoxy polyethylene glycol and the like, theorthoacetates and chloroorthoacetates of methoxy poly-1,2-propyleneglycol, tri(ethoxy poly-1,3-propylene glycol)ortho-2,3-dimethylbutyrate, tri(ethoxy polypropylene glycol)orthopropionate, tri(butoxy poly-1,2-propylene glycol) orthoacetate,tri(butoXy poly[mixed oxyethylene-oxy-1,2-propylene]-glycol)orthoacetate, tri(butoxy poly[mixed oxyethyleneoxy-1,2-propylene]glycol)orthopropionate, tri- (ethoxy poly[mixedoxyethyleneoxy-1,2-propylene]glycol) orthochloroacetate, theorthoacetate and chloroorthoacetate of tetrahydrofurfuryl alcohol, theorthopropionate of u-tetrahydrofurfuryl alcohol, the orthobutyrate of B-tetrahydrofurfuryl alcohol, the orthoacetate and orthochloroacetate ofN,N-diethyl isopropanolamine, N,N-dimethyl ethanol amine, andN-methyl-2-piperidylmethanol, the orthoacetate and orthochloroacetate ofN,N-diethyl- 2-piperazinylethanol, the orthopropionate ofN,N-dimethylethanol amine, the orthobutyrate of N,N-dipropylpropanolamine methoxyethyl ortho-2-methylbutyrate, tri- (butoxydipropylene glycol) ortho-2-methylpropionate, the ethoxy polyethyleneglycol orthoester of 3-ethylpropionic acid, and the like.

This novel process comprises the slow addition of a dihaloalkene to abasic hydroxy compound such as an alkali metal alcoholate which has anelectron donating atom in the beta or gamma position. The novel processmay be illustrated by the following reaction between the sodiumalcoholate of methoxyethanol and vinylidene chloride to produce ketenedi(methoxyethyl) acetal Since this reaction will only proceed using abasic alcoholate of a compound which is characterized by an electrondonating atom, e.g., oxygen, in the beta or gamma position. It ispostulated that perhaps the unusual activity of the alcoholate in thisnovel synthesis results from a quasicyclic intermediate which is formedby the alcoholate, and which accordingly markedly increases the basicityof the alkoxide oxygen. This is illustrated by the followingSodium-,8-a1k0xyalcol1olate It is known that S-membered and 6-memberedrings are most stable, and thus it would be reasonable to assume thatthe activation of the electron donative atom, in this case the alkoxideoxygen would be greatest when it existed in the beta or gamma, sincethese positions would result in five and six membered quasicyclesrespectively. This theory is supported by the fact that alcoholateshaving an electron donative atom in the alpha or delta positions willnot produce ketene acetals or orthoesters despite the variance ofreaction conditions. Of course a quasicyclic intermediate of thesealcoholates would be four membered or seven membered, respectively, andaccordingly much less stable. Similarly hydrocarbyl alcoholates exhibitsno reactivity in the novel process of this invention.

Accordingly, although applicant does not wish to bind himself by thetheory proposed above, it is deemed to illustrate the singular natureand surprising efiicacy of the instant process which will become betterunderstood by a consideration of the following disclosure and examples.

Both the ketene acetals and orthoesters of this invention are preparedin substantially the same manner. The products obtained will depend uponthe mole ratios of reactants employed as well as upon the steric natureof these reactants. In order to produce the novel ketene acetals of thisinvention, it is desirable to employ approximately two moles of thealkali metal alcoholate for each mole of the dihaloalkene, and toconduct the reaction in an inert solvent medium. Thus, for example,ketene methoxyethyl acetal is produced from the sodium alcoholate ofethylene glycol monomethyl ether and vinylidene chloride as follows:

CH OCH 9 63 inert )CHZO Na CH1=CCI1 solvent (OHaOCHzCHzO)1 0:011; 2NaClHowever, when it is desired to form the orthoester the alkali metalalcoholate is employed in a solution of the alcoholic hydroxy compoundfrom which it is derived, the said solution providing at least oneadditional mole of the alcoholic hydroxy compound. Thus, orthoesterformation may occur when this additional mole of alcoholic hydroxycompound combines with the ketene acetal (CH OCH CH O C=CH +CH OCH CH OH(CH OCH CH O CCH The orthoester formation is catalyzed by acid, and

hence although often the reaction may be directed to the orthoesterproduct by using a greater mole ratio of basic alcoholate todihaloalkene, the addition of acid to the original reaction mixture orto a mixture of ketene acetal and alcoholate will promote the productionof the orthoester as the final product. Suitable acids for this purposeare the mineral acids such as sulfuric acid, phosphoric acid, andsulfonic acid. It is apparent from this reaction that if the solventmedium is an alcohol other than that from which the alkali metalalcoholate was produced, that a mixed orthoester product will result. Ofcourse, a mixed acetal or orthoester product may also be produced byusing a mixture of alkali metal alcoholates.

Steric considerations will also effect this second reaction to form theorthoester product. For example, if the sodium alcoholate of propyleneglycol monomethyl ether is reacted with vinylidene chloride, inaccordance with this invention, even if the solvent medium employed isthe alcohol, i.e., propylene glycol monoethyl ether, rather than aninert solvent, the steric effect of the pendant methyl group may be suchas to halt the reaction when the ketene methoxypropyl acetal issynthesized and impede production of the orthoester. Since theproduction of the orthoester from the ketene acetal is acidcatalyzed, itmay be necessary to further acidity the reaction mixture in the presenceof excess alcohol, in order to drive the reaction to the methoxypropylorthoacetate product. Alternatively, if the sodium alcoholate ofethylene glycol monomethyl ether is reacted with vinylidene chloride,the steric hindrance is greatly reduced and the reaction will readilyproceed to the methoxyethyl orthoacetate if conducted in the presence ofethylene glycol monomethyl ether. In fact to halt this reaction beforeproduction of the orthoester and produce ketene methoxyethyl acetal, thereaction must he conducted in an inert solvent and the prescribed two toone mole ratio of sodium alcoholate to vinylidene chloride should beobserved.

The reaction is accompanied by an exotherm and completion of thereaction is signalled by the termination of the temperature rise.

Suitable alcoholic hydroxy compounds which may be employed in preparingthe novel ketene acetals and orthoesters of this invention are similarin structure to the ketene acetal and the orthoester products, and maybe identified by the presence of an electron donative atom in theposition beta or gamma to the alcoholic hydroxy group. These alcoholichydroxy compounds are represented by the formula:

wherein R R and X have the designations as defined above. Thesecompounds include the monoalkyl ethers of 1,2-a1kylene glycols such asethylene glycol mono methyl ether, ethylene glycol monoethyl ether,ethylene glycol monobutyl ether, ethylene glycol monohexyl ether,1-phenoxy-2-ethanol, l-benzyloxy-Z-ethanol, l-methoxyl-phenyl-Z-ethanol,l-ethoxy-1,2-dimethyl-ethanol, l-butoxy-2-benzyl-2-ethanol,l-phenoxy-1methyl-2-ethanol, 1- hexoxy-Z-methyl-2-ethanol, and the like;the monoalkyl ethers of l,3-glycols such as l-methoxy-3-propanol, 1-butoxy-3-propanol, l-phenoxy-3-propanol, l-phenoxy-lmethyl 3-propanol,1-butoxy-2-phenyl 3-propanol, 1- methoxy-3,3-dimethyl-3-propanol,1-ethoxy-2,2-dimethyl- 3-propanol, 1-methoxy-2-benzyl-3-propanol; thedialkyleneoxy, and polyalkyleneoxy compounds such as diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, di-1,2- propylene glycol monomethyl ether, anddi-l,3-propylene glycol monomethyl ether, di-1,2-propylene glycolmonobutylether, di-1,3-propylene glycol monohexyl ether, di-2,3-butyleneglycol monoethyl ether, di-1,3-butylene glycol monoethyl ether, and thelike; poly(oxyethylene) glycol monoethyl ether, poly(oxyethylene) glycolmonobutyl ether, poly(oxy-LZ-proPylene) glycol monobutyl ether,poly(oxy-1,3-propylene) glycol monomethyl ether, poly(oxy 1,2-butylene)glycol monobutyl ether, poly (oxy-2,3-butylene) glycol monoethyl ether,poly(mixed oxyethylene-oxy-1,2-propylene) glycol monobutyl ether,poly(mixed oxyethylene-oxy-1,3-propylcne) glycol monoethyl ether and thelike; 3-tetra'hydrofurfuryl alcohol, 2- tetrahydrofurfuryl alcohol,N,N-dimethylethanolamine, N,Ndiethylethanol amine, N-methyl-3-propanolamine, N-ethyl-N-butylethanolamine, N-butyl-3-piperidinyl alcohol,N-ethyl-3-piperizinyl alcohol, and the like.

The dihaloalkenes which are suitable for use in this invention includethe dihalo-a-olefins of the formula:

wherein Y is halogen or hydrogen and R is hydrogen or alkyl with theproviso that at least two Y moieties are halogen and providing if R isalkyl at least one Y moiety is hydrogen. Thus these reactants include1,1-dihalo-aolefins, 1,2-dihalo-a-olefins, and 1,1,2-trihaloethane. Bothcis-and trans forms of the 1,2-dihalo-m-olefins may be employed.Accordingly, suitable dihalo-a-olefins include vinylidene chloride,l-chloro-lbromoethane, 1-chl0ro-2- bromoethene, 1,1,2-trichloroethene,1,2-dichloroethene, 1,2-diromoethene, l,l-dichloro-l-prop-l-ene,1,1-dichlorobut-l-ene, 1,1-dichloropent l-ene, 1,2-dichlor0pent-1- ene,1,1-dichlorohex-1-ene, l-chloro-l-bromohex-l-ene,l,l,Z-trichloro-l-prop-1-ene, l-chloro 1,2-dibromoprop- .l-ene,l,l,Z-trichloro-l-but-l-ene, 1,1,2-pent-l-ene, 1,1,2-trichlorohex-l-ene, 1,1-dichloro Z-phenylcthene,1,1-dichloro-Z-benzylethene, 1,1-dichloro Z-benzylprop-l-ene, 1, l-dichloro-2-bromoethene, 1,2-dichloroprop-1-ene, 1,1-

dichloro-2-bromopentene, and the like. Preferred halo-uolefins are thosewherein halogen is chlorine or bromine,

bon atoms such as vinylidene chloride, 1,1,2-trichloroethene,1,1-dichloroprop-1-ene, 1,1,2-trichloroprop-1-ene,1,1-dichlorobut-l-ene, l,1,2-trichlorobut-l-ene, and the like.

A direct synthesis of mixed ketone acetals may be achieved by analternate route by which a full yield of the mixed product can beobtained. Of course, by proceeding to synthesize mixed ketene acetals byutilizing a mixture of basic alcoholates in the procedure as above, astatistical yield of any single mixed ketene acetal bearing differentetheric moieties corresponding to the basic alcoholates will beobtained. Accordingly there is provided by this invention a directsynthetic method for producing mixed ketene acetals which methodcomprises contacting a basic alcoholate, derived from an alcoholichydroxy compound as hereinbefore described, and a fl-halo-a,p-a1kenylether of the formula:

wherein R is hydrogen, alkyl, or haloalkyl preferably of up to 3 carbonatoms, wherein B is halogen, and wherein R represents a radical of thescope of R defined above or is a radical having an electron donativeatom in the gamma or beta position said radical corresponding to theformula:

loillliilm) 1' h Liu J...

alcoholate and one etheric moiety corresponding to the R substituent ofthe haloalkenyl ether:

wherein R R R R X, B, and m are as above designated. These keteneacetals may of course be further reacted with an additional mole ofalcoholic hydroxy compound, in the presence of an acidic catalyst ifnecessary, to produce the mixed orthoester product.

The fl-halo-a,;3-alkenyl ethers which can be employed in the directacetal synthesis above may be synthesized by contacting an a,/i-alkenylether With halogen the presence of a dihydrohalogenating agent such as atertiary amine, e.g., triethylamine, pyridine, or N,N-dimethylaniline.The synthesis of a-bromoethenyl ether from vinyl ethyl ether, in thepresence of N,N-dirnethyl aniline is illustrative Accordingly, suitableB-halo-u,B-alkenyl ethers useful in the direct mixed acetal synthesisinclude a-bromoethylenyl ethyl ether, a-chloroethenyl ethyl ether,ot-ChlOI'O-ot,j3- butenyl ethyl ether, a-chloroethenyl hexyl ether, 0:-chloro-a,fl-propenyl phenyl ether, ot-chloroethenyl benzyl ether,a-chloroethenyl p-tolyl ether, a-bromoethenyl 2- (N,N-dimethylamino)ethyl ether, a,'y-dibromo-a,B-propenyl-3-tetrahydrofuranyl ether, theot-chloroethenyl ether of butoxy poly(oxyethylene) glycol, and the like.

The direct mixed acetal synthesis proceeds under essentially the sameconditions as does the acetal.

The novel process for producing ketene acetals and orthoesters isadvantageously conducted by slowly adding the dihalo-a-olefin, withstirring to a strongly basic solution of an alcoholate of the describedhydroxy compound in the alcohol.

The direct mixed acetal synthesis may be similarly carried out, in whichcase the ot-halo-a,/3-alkenyl ether is slowly added to a basic solutionof the alcoholate. tIf desired, the reaction alcoholate mixture may bemaintained in an inert organic solvent. This strongly basic solution maybe conventiently prepared by mixing the compound with a Group Ia or IIametal or a metal hydroxide thereof. Preferred operatives are sodiummetal or sodium hydroxide. When preparing the alkali metal alcoholatefrom the metal hydroxide, the water of reaction and the water of thehydroxide solution is removed from the alcoholate by azeotropicdistillation. The lower sodium alcoholates such as sodium methylate andsodium ethylate can also be employed. Potassium metal is difficult tohandle as are metallic rubidium and cesium and, therefore, would not bepreferred for preparation of these basic alcoholates though they wouldbe operative. Potassium hydroxide when used in the place of sodiumhydroxide gives an uncontrolled reaction and is, therefore, notpreferred, although not inoperative. The basic solution of the alcoholiccompound is prepared by the addition of the metal or metal hydroxide, asdescribed above, such as sodium metal or sodium hydroxide, to the saidalcoholic compound. In accordance with this invention and depending uponthe product desired as hereinbefore set forth, the said alcoholate maybe prepared in a solution of an excess of the alcohol or in an inertsolvent such as diethylene glycol dirnethyl ether, tetrahydrofuran,xylene, n-heptane and the like.

Inasmuch as the reaction produces an exotherm, the temperature of thereaction medium may be conveniently controlled by a slow measuredaddition of the halide compound accompanied by stirring to assure themixture of the reactants. The reaction is accompanied by a concomitantprecipitation of the alkali metal chloride, e.g., sodium chloride,corresponding to the metal used to basify the hydroxy compound. Thedirect mixed ketene acetal synthesis also produces the salt precipitate.This yield may conveniently be employed to calculate the completeness ofthe reaction. The reaction is preferably carried out under refluxconditions, and it is preferred that the addition rate of the chloridecompound not be greater than the capacity of the reflux condenser underthe prevailing conditions. The completion of the reaction is signalledby a termination of the exotherm.

Normally the starting temperature and starting pressure for the novelprocess are not narrowly critical. Ambient temperatures are suitable atthe start of the reaction. The temperature increase resulting from theexotherm is desirably controlled, as hereinbefore described, so as notto cause the reaction to exceed the reflux capacity. Normally, thetemperature is not permitted to exceed about 200 C. under operatingconditions although no criticality is imputed. Pressure is not criticaland the reaction may be conducted at subatmospheric, atmospheric orsuperatmospheric pressure.

The reaction of the novel process is suitably conducted under an inertatmosphere such as nitrogen, since air will cause oxidation of thestrongly basic reactants.

The ketene acetals of this invention will give high polymers in thepresence of even a small amount of acid, and will undergo polymerizationto form a film on the surface of a glass container by virtue of acidicsurface of the glass. Accordingly, storage of ketene acetals isgenerally facilitated by avoiding acidic conditions in the storingcontainer. Washing of such containers with alkali prior to introductionof the ketene acetal is hence preferred.

The ketene acetals of this invention may be satisfactorily andefficiently polymerized using an acidic catalyst but these keteneacetals do not respond to free radical catalysts of the peroxide type.Suitable catalysts include the metal chlorides and non-ionic acids suchas calcium chloride, cadmium chloride, aluminum chloride, stannicchloride, zinc chloride, boron fluoride and the like. The catalysts arepreferably used in anhydrous form, and the polymerization proceeds atroom or slightly elevated temperatures, i.e., up to about C. Thepolymerization proceeds through the unsaturation of the acetal toproduce a polymer having a basic repeating unit as follows as forexample in the case of ketene di(Z-methoxyethyl acetal):

\LII (I)C2H5OCH3/ This polymer structure, of course may be extrapolatedto encompass those ketene acetals generally represented by Formula IIsupra.

In addition, the acidic catalysts above may also be utilized to catalyzethe copolymerization of the novel ketene acetals of this invention withother olefinic monomers which respond to ionic polymerization. Preferredcomon omers are the vinyl alkyl ethers wherein said alkyl portioncontains from 2 to about 18 carbon atoms, preferably 2 to 8 carbonatoms. Illustrative of these vinyl alkyl ethers are vinyl ethyl ether,vinyl butyl ether, vinyl pentyl ether, vinyl hexyl ether, vinylZ-methylpentyl ether, vinyl 2-ethylhexyl ether, vinyl octyl ether, vinyldodecyl ether, vinyl octadecyl ether and the like. By appropriate choiceof the ketene acetal and the vinyl alkyl ether comonomer these polymersmay be rendered water soluble or water insoluble by adjusting the numberof hydrophilic ethyleneoxy groups in the polymer. Likewise the keteneacetal homopolymers may also be water soluble depending upon the amountof ethyleneoxy linkages in the ketene acetal.

The orthoesters of the invention may be used as plasticizers and alsohave Wide use as intermediates. Table I below summarizes the evaluationof methoxy diethylene glycol orthoacetate and tetrahydrofurfurylorthoacetate as plasticizers in polyvinyl chloride.

TABLE I.EVALUATION OF ORII-IOACETA'IES AS PLAS TICIZERS FOR VINYLCHLORIDE POLYMERS Methoxy di- 'Ietrahydrofurethylene glycol furylorthoorthoacetate acetate Plasticizer, concentration parts per hundred50 50 Durometer A hardness 61 68 T4, (3. 6 9 TB, 0. 22 -14 Volatility,24 hrs., 70 0., 20 mil weight percent 27. 6 28. 1 Oil extraction, K 6. 72. 2 Water extraction, percent 21. 6 4. 8 Sweat out after 2 weeks SlightNone I Durometer A harduess=an indentation measurement of hardnessobtained with the Shore Durometer A head.

2 T4=points corresponding to 10,000 pounds per square inc respectivelyon a stifiness temperature curve obtained in accordance with theprocedure set forth in the manual of ASTM D1043-51.

3 Tn=Brittle temperature, the temperature obtained by means of lowtemperature impact test accordlng to the procedure set forth in themanual of ASTM D746-52T.

4 Volatility loss=value obtained in accordance with the procedure in themanual of ASTM D1023-521.

5 Oil extraction= determines the tendency of a plasticizer to beextracted by mineral oil. A four-mil film is immersed in mineral oil at50 C. for a sufficient time to produce a weight loss of between 3 and 10percent. The results are reported in terms of an extraction constant K.

where W =original weight in grams, Wz=final weight in grams,

a=total area of plaque, in square meters,

t=time in hours.

6 Water extraetion=determines the tendency of a plasticizer to beextracted by water set forth by the procedure set forth in the AmericanSociety of Testing Materials, Bulletin No. 183, July, 1952. Expressed aspercent by weight of loss from test specimen.

Parts Polyol 100 Water 4.00 Silicone surfactant 2.00 Stannous octoate0.30 Tolylene diisocyanate 49.7

Ketene di 2- (N,N-dimethylamino ethyl] acctal 'lhe polyol employed was aglycerol propylene oxide adduct having an average molecular weight ofabout 3000 and having a hydroxyl number of about 55.

For usage of this compound in three batches, see second paragraph,below.

The polyol, silicone surfactant, water and the ketonedi[2-(N,N-dimethylamino)ethyl]acetal were mixed using a drill pressstirrer in a 2-liter stainless steel beaker for 55 seconds.

The stannous octoate was added and the mixture stirred for an additional5 seconds before the tolylene diisocyanate was added. Stirring wascontinued for a 5 to 8 second period after which time the mixture waspoured into a cardboard mold. The time required for the bun to rise to 1to full height is defined as rise time. Three batches of foamingformulation were prepared using 0.05, 010 and 0.50 part by weight ofketene di[2-(N,N-dimcthyl amino)cthyl] acetal respectively. In additionone control formulation containing no amine catalyst was prepared. Risetimes were as follows:

Rise time (sec.)

A mixture of the sodium alcoholate of propylene glycol monomethyl etherin the alcohol was prepared by reacting 11.1 moles of propylene glycolmonomethyl other (1000 grams) with 4.35 moles of metallic sodium grams).To this mixture was slowly added, with stirring, 3.10 moles ofvinylidene chloride under a nitrogen atmosphere. During the addition ofthe vinylidene chloride the temperature of the reaction mixtureincreased from 90 to C. with the concomitant precipitation of sodiumchloride. The reaction mixture was then filtered to yield a tan coloredliquid filtrate and solid sodium chloride.

The solid was washed several times with anhydrous ether and was-oven-dried to give 235 grams of sodium chloride which calculated as a92.5 percent yield of sodium chloride based on the sodium used in thereaction.

The liquid filtrate was vacuum distilled to yield a distillate of 206grams of the ketene acetal derivative of propylene glycol monomethylether which is ketene di(2- methoxypropyl) acetal (45.6 percent yield)having a boiling point of 87-95 C. at 5.0 millimeters of mercury, and 58C. at 3 millimeters of mercury. The distillate was analyzed as follows:

Analysis.-Calculated for C H O C, 58.9; H, 9.9; O, 31.3. Found: C, 58.8;H, 10.1; 0, 32.2. Molecular weight: Calculated 204. Found:2.4(Menzies-Wright in benzene).

The infrared spectrum showed a very strong band at 1650 cm. indicating(C CH EXAMPLE II Two drops of 85 percent phosphoric acid were added to asolution 0.25 mole of the ketene di(2-methoxypropyl) acetal (51.0 grams)and 0.25 mole of propylene glycol monomethyl ether (22.5 grams), causingthe term perature to rise from 20 to 70 C. The mixture was permitted tostand overnight at room temperature after which two small pellets ofpotassium hydroxide were added to the solution. The solution was vacuumdistilled to yield, as the major fraction, methoxy propylene glycolorthoacetate which was analyzed as follows:

Analysis.-Calculated for C H O C, 57.1; H, 10.3. Found: C, 56.9; H,10.3. Molecular weight: Calculated 294. Found: 290(Menzies-Wright inbenzene).

The infrared spectrum revealed that characteristic OH, C=O, C==CHabsorption bands were absent.

EXAMPLE III A mixture of the sodium alcoholate of dipropylene glycolmonomethyl ether in the alcohol was prepared by reacting 3.37 moles ofdipropylene glycol monomethyl ether (500 grams) with 1.3 moles ofmetallic sodium (30 grams). To this mixture was slowly added, withstirring, 1.3 moles of vinylidene chloride under a nitrogen atmosphere.During the addition of the vinylidene chloride the temperature of thereaction mixture increased from 95 to C. with the concomitantprecipitation of sodium chloride. The reaction mixture was then filteredto yield a liquid filtrate and solid sodium chloride.

The solid was washed and oven dried to give 71 grams of sodium chloridewhich calculated as a 93 percent yield of sodium chloride based on thesodium used in the reaction.

The liquid filtrate was vacuum distilled to yield 42 grams of adistillate of the orthoacetate of dipropylene glycol monomethyl ether(13.8 percent yield) having a boiling point of 166 to 186 C. at 5.0millimeters of mercury. A distillate fraction boiling at 166186 C. atmillimeters of mercury was analyzed as follows:

Analysis.Calculated for C H O C, 59.1; H, 10.3; 0, 30.8. Found: C, 58.2;H, 10.4; 0, 35.1. Molecular weight: Calculated 468. Found: 388.

The infrared spectrum showed a small amount of carbonyl absorptionindicating some chemical breakdown.

EXAMPLE IV A mixture of the sodium alcoholate of ethylene glycolmonoethyl ether in the alcohol was prepared by reacting 11.1 moles ofethylene glycol monoethyl ether (1000 grams) with 4.35 moles of metallicsodium (100 grams). To this mixture was slowly added, with stirring,2.58 moles of vinylidene chloride under a nitrogen atmosphere duringwhich the temperature of the reaction mixture increased from 100 to 160C. with the concomitant precipitation of sodium chloride. The reactionmixture was then filtered to yield a liquid filtrate and solid sodiumchloride.

The solid was washed and oven dried to give 230 grams of sodium chloridewhich calculated as a 91 percent yield of sodium chloride based on thesodium used in the reaction.

The liquid filtrate was vacuum distilled to yield 362 grams of adistillate of the orthoacetate of ethylene glycol monoethyl ether (56.6percent yield) having a boiling point of 110 to 129 C. at 2 to 3millimeters of mercury. The distillate fraction boiling at 98 to 100 C.at 0.5 millimeter of mercury was analyzed as follows:

Analysis.-Calculated for C H O C, 57.1; H, 10.3. Found: C, 57.2; H,10.3. Molecular weight: Calculated 294. Found: 281.

The infrared spectrum showed an absence of OH, C 0, and C CH absorptionbands.

EXAMPLE V A mixture of the sodium alcoholate of diethylene glycolmonomethyl ether in the alcohol was prepared by reacting 8.34 moles ofdiethylene glycol monomethyl (1000 grams) with 4.35 moles of metallicsodium (100 grams). To this mixture was slowly added, with stirring,2.58 moles of vinylidene chloride under a nitrogen atmosphere duringwhich the temperature of the reaction mixture increased from 85 to 185C. with the concomitant precipitation of sodium chloride. The reactionmixture was then filtered to yield a liquid filtrate and solid sodiumchloride.

The solid was washed and oven dried to give a quantitative yield ofsodium chloride based on the sodium used in the reaction.

The liquid filtrate was vacuum distilled to yield 255 grams ofdistillate of the orthoacetate of diethylene glycol monomethyl ether(30.5 percent yield) having a boiling point of 184 to 196 C. at 2.0millimeters of mercury. The distillate boiling at 170 to 172 C. at 0.5millimeter of mercury was analyzed as follows:

Analysis.-Calculated for C H O C, 53.5; H, 9.5. Found: C, 52.1; H, 9.5.Molecular weight: Calculated 384. Found: 376.

The infrared spectrum showed an absence of the OH, C O, and C=CHabsorption bands.

EXAMPLE VI A mixture of the sodium alcoholate of tetrahydrofurfurylalcohol in the alcohol was prepared b reacting 9.80 moles oftetrahydrofurfuryl alcohol 1000 grams) with 3.26 moles of metallicsodium (75 grams). To this mixture was slowly added, with stirring, 2.06moles of vinylidene chloride under a nitrogen atmosphere during whichthe temperature of the reaction mixture increased from 100 to 181 C.with the concomitant precipitation of sodium chloride. The reactionmixture was then filtered to yield a liquid filtrate and solid sodiumchloride.

The solid was washed and oven dried to give 191 grams of sodium chloridewhich calculated as a percent yield of sodium chloride based on thesodium used in the reaction.

The liquid filtrate was vacuum distilled to yield 287 grams ofdistillate of the orthoacetate of tetrahydrofurfuryl alcohol (53.4percent yield) having a boiling point of 178 to 185 C. at 1.5millimeters of mercury. The distillate fraction boiling at 151 to 154 C.at 0.5 millimeter of mercury was analyzed as follows:

Analysis.Calculated for C H O C, 61.9; H, 9.1. Found: C, 62.3; H, 9.3.Molecular weight: Calculated 330. Found 326.

The infrared spectrum showed an absence of OH, C O, and C CH absorptionbands.

EXAMPLE VII A mixture of the sodium alcoholate of tetrahydrofurfurylalcohol in the alcohol was prepared by reacting 4.90 moles oftetrahydrofurfuryl alcohol (500 grams) with 1.09 moles of metallicsodium (25 grams). To this mixture was slowly added, with stirring, 0.70mole of 1,2,2- trichloroethene under a nitrogen atmosphere during whichthe temperature of the reaction mixture increased from 93 to 117 C. withthe concomitant precipitation of sodium chloride. The reaction mixturewas then filtered to yield a liquid filtrate and solid sodium chloride.

The solid was washed and oven dried to give 53 grams of sodium chloridewhich calculated as a 83 percent yield of sodium chloride based on thesodium used in the reaction.

The liquid filtrate was vacuum distilled to yield 27 grams of adistillate of the orthomonochloroacetate of tetrahydrofurfuryl alcohol(13.6 percent yield) having a boiling point of 145 to 160 C. at 1.5millimeters of mercury. The distillate was analyzed as follows:

Analysis.Calculated for C H O Cl: C, 56.0; H, 8.0; Cl, 9.8. Found: C,55.8; H, 8.2; Cl, 9.6. Molecular weight: Calculated 364. Found 321.

The infrared spectrum analysis showed an absence of -OH, C O, and C=CHabsorption bands.

EXAMPLE VIII A mixture of the sodium alcoholate of propylene glycolmonomethyl ether in the alcohol was prepared by reacting 11.1 moles ofpropylene glycol monomethyl. ether 1000 grams) with 3.0 moles ofmetallic sodium (69 grams). To this mixture was slowly added, withstirring, 1.8 moles of 1,1-dichloro-1-propene under a nitrogenatmosphere during which the temperature of the reaction mixtureincreased from to C. with the concomitant precipitation of sodiumchloride. The reaction mixture was then filtered to yield a liquidfiltrate and solid sodium chloride.

The solid was washed and oven dried to give 157 grams of sodium chloridewhich calculated as a 90 percent yield of sodium chloride based on thesodium used in the reaction.

The liquid filtrate was vacuum distilled to yield 27.0 grams of adistillate of the methylketene di(2-methoxy propyl) acetal (8.3 percentyield) having a boiling point of 81 C. at 0.1 millimeter of mercury. Thedistillate was analyzed as follows:

Analysis.Calculated for C H O C, 60.6; H, 10.1. Found: C, 60.4; H, 9.9.Molecular weight: Calculated 218. Found 205.

The infrared spectrum showed a strong C=C doublet at 1650 cm. and 1620cm.

EXAMPLE IX A mixture of the sodium alcoholate of the 1,2-propylene oxideadduct of glycerol having a molecular weight of about 3000 was preparedby reacting 0.5 mole of the said adduct (1500 grams) with 0.65 mole ofmetallic sodium (15 grams). To this mixture was slowly added, withstirring, 1.03 moles of vinylidene chloride under a nitrogen atmosphereduring which the temperature of the reaction mixture increased from 120to 130 C. with the concomitant precipitation of sodium chloride. Thereaction mixture was then filtered to yield a liquid filtrate and solidsodium chloride. The solid sodium chloride was not collected.

The grey-tan residue product had a viscosity of 770 cps. at 25 C. ascompared with the adduct itself which has a viscosity of 480 cps. at 25C.

Infrared spectrum analysis of this residue product revealed a mediumsharp peak at 1650 cm? which was postulated to be the ketene acetal(C=CH absorption, and identified the product as the ketene acetal ofpropylene oxide adduct of glycerol.

EXAMPLE X A mixture of the sodium alcoholate of polyethylene oxidehaving a molecular weight of about 400 in the alcohol was prepared byreacting 2.50 moles of the said polymer (1000 grams) with 3.75 moles ofsodium hydroxide (150 grams). Water was removed from the solution byvacuum stripping at 110 C. and 5.0 millimeters of mercury for 2 hours.To this mixture was slowly added, with stirring, 2.76 moles ofvinylidene chloride under a nitrogen atmosphere during which thetemperature of the reaction mixture increased from 90 to 142 C. with theconcomitant precipitation of sodium chloride. The reaction mixture wasthen filtered to yield a liquid filtrate and solid sodium chloride whichwas removed but not Weighed. The liquid filtrate was refined with 30grams of magnesium silicate and vacuum stripped for 2 hours at 90 C. andfiltered to yield the residue product which was analyzed as follows:

Average hydroxyl number: 169.

Analysis.-Found: C, 52.8; H, 9.10; O, 37.12. Molecular weight: Found661.

The infrared spectrum showed a medium sharp absorption band at 1740 emfindicating C=O, and a medium sharp band at 3450 emf indicating -OH.

EXAMPLE XI A mixture of the sodium alcoholate of N,N-dimethyl ethanolamine in the alcohol was prepared by reacting 2.0 moles of the saidamine (178 grams) with 4.35 moles of metallic sodium (100 grams), in 200grams of xylene. To this mixture was slowly added over a 27 minuteperiod with stirring, 1.24 moles of vinylidene chloride (120 grams)under a nitrogen atmosphere during which the exotherm of the reactionmixture was sporadic and rapid from 130 to 142 C. with the concomitantprecipitation of sodium chloride. The reaction mixture was then filteredto yield a liquid filtrate and solid sodium chloride.

The solid was washed and oven dried to give 100 grams of sodium chloridewhich calculated as a 93.5 percent yield of sodium chloride based on thesodium used in the reaction.

The liquid filtrate was vacuum distilled to-yield a higher boilingfraction boiling at 90-91 C. at 2.0 millimeters of mercury.

Ana[ysis.Calcd for C H N O C, 59.4; H, 10.95; N, 13.84. Found: C, 60.5;H, 10.96; N, 13.74. Molecular Weight: Calcd: 202. Found: 201(Menzies-Wright in benzene).

The infrared spectrum showed a very strong absorption at 1640 cm.- whichcorresponds to a ketene acetal type absorption and identified theproduct as ketene di[2-(N,N- dimethylamino ethyl] acetal.

EXAMPLE XII A mixture of the sodium alcoholate of tetrahydrofurfurylalcohol in diethylene glycol dimethyl ether was prepared by reacting2.() moles of tetrahydrofurfuryl alcohol (204 grams) with 2.0 moles ofsodium metal (46.0 grams) in 408 grams of diethylene glycol dimethylether. To this mixture was added slowly, with stirring, 1.56 moles ofvinylidene chloride (150 grams) under a nitrogen atmosphere. During theaddition or the vi..yliuene chloride, the temperature of the reactionmixture increased from C. to 140 C. with concomitant precipitation ofsodium chloride. The reaction mixture was then filtered to yield aliquid filtrate and solid sodium chloride.

The solid was washed and oven dried to give a quantitative yield ofsodium chloride based upon the sodium used in the reaction.

The liquid filtrate was vacuum distilled to yield grams of distillate ofketene Z-tetrahydrofurfuryl acetal (0.483 mole corresponding to a 48.3percent yield) having a boiling point of 109 to 110 C. at 2.0millimeters of mercury. The distillate was analyzed as follows:

Analysis.-Calculated for C H O C, 63.10; H, 8.77. Found: C, 62.93; H,8.88. Molecular weight: Calculated 228. Found: 223.

Infrared spectrum analysis showed a very strong C=CH absorption band at1640 cmr and indicated no -OH absorption.

EXAMPLE XIII The sodium alcoholate of Z-methoxyethanol was prepared byreacting 4.0 moles of Z-methoxyethanol (304 grams) with 4.0 moles ofmetallic sodium (92 grams) in 500 grams of diethylene glycol dimethylether as solvent. To this mixture was slowly added, with stirring, 243grams of vinylidene chloride (2.51 moles) under a nitrogen atmosphere.During the addition of the vinylidene chloride the temperature of thereaction mixture: increased from to 170 C. with the concomitantprecipitation of sodium chloride. The reaction mixture was then filteredto yield a liquid filtrate and solid sodium chloride.

The solid was washed several times with anhydrous ether and was ovendried to give 225 grams of sodium chloride which calculated as a 96percent yield of sodium chloride based on the sodium used in thereaction.

The liquid filtrate was vacuum distilled to yield a distillate of 181grams of the ketene di(2*methoxyethyl) acetal (51.4 percent yield)having a boiling point of 78-80 C. at 2.0 millimeters of mercury. Thedistillate was analyzed as follows:

Analysis.-Calculated for C H O C, 54.5; H, 9.16. Found: C, 54.5; H,9.05. Molecular weight: Calculated 176. Found: 178 (Menzies-Wright inbenzene).

The infrared spectrum showed a very strong C=C absorption at 1640 cm?and characteristic hydroxyl absorption was completely absent. Thenuclear magnetic resonance spectrum was in agreement wtih the keteneacetal structure.

EXAMPLE XIV The sodium alcoholate of 3,4-dihy dro-2H-pyran-2- methanolwas prepared by reacting 1.94 moles of 3,4-dihydro-2H-pyran-2-methanol(226 grams) with 1.94 moles of metallic sodium (43 grams) in grams ofdiethylene glycol dimethyl ether as solvent. To this mixture was slowlyadded, with stirring, 1.24 moles of vinylidene chloride (120 grams)under a nitrogen atmosphere. During the addition of the vinylidenechloride the temperature of the reaction mixture increased Irom 125 toC. with the concomitant precipitation of sodium chloride. The reactionmixture was then filtered to yield a liquid filtrate and solid sodiumchloride.

The solid was washed several times with anhydrous ether and was ovendried to give 104 grams of sodium chloride which calculated as an 89percent. yield of sodium chloride based on the sodium used in thereaction.

The liquid filtrate was vacuum distilled to yield a distillate or 71grams of the ketene di(3,4-dihydro-2H-pyran- Z-methoxy) aceta] (28.4percent yield) having a boiling point of 149150 C. at 2.4 millimeters ofmercury. The distillate was analyzed as follows:

Analysis.Calculated for C H O C, 66.7; H, 7.94. Found: C, 66.5; H, 8.05.Molecular weight: Calculated 252. Found: 236 (Menzies-Wright inbenzene).

The infrared spectrum showed a very strong C=C absorption at 1640 cm.-and characteristic hydroxy absorption was completely absent.

EXAMPLE XV The sodium alcoholate of 2-meth0xyethanol was prepared byreacting 2.0 moles of 2-methoxyethanol (152 grams) with 2.0 moles ofmetallic sodium (46 grams) in a stirred flask containing 50 grams ofdiethylene glycol dimethyl ether as solvent. The sodium was dissolvedover a 2.5 hour period at a temperature of 120 to 155 C. To this mixturewas slowly added, with stirring, 0.62 mole of cis-l,2-dichloroethenegrams) over a 22 minute period while maintaining the mixture under anitrogen atmosphere. During the addition of the cis-1,2-dichloroethenethe temperature of the reaction mixture increased from 140 to 178 C.with the concomitant precipitation of sodium chloride. To aid in coolingthe reaction mixture, 100 milliliters of diethyl ether was added. Thereaction mixture was then filtered to yield a liquid filtrate and solidsodium chloride.

The solid was washed several times with anhydrous ether and was ovendried to give 74 grams of sodium chloride which calculated as a 63.3percent yield of sodium chloride based on the sodium used in thereaction.

The liquid filtrate was vacuum distilled to yield a distillate of 82grams of the ketene di(Z-methoxyethyl) acetal (46.6 percent yield)having a boiling point of 80- 81 C. at 1.7 millimeters of mercury. Thedistillate was analyzed as follows:

Analysis.Calculated for C H O C, 54.5; H, 9.16. Found: C, 54.5; H, 9.05.Molecular weight: Calculated 176. Found: 178 (Menzies-Wright inbenzene).

The infrared spectrum showed a very strong C=C absorption at 1640 cmfThe nuclear magnetic resonance spectrum was in agreement with the keteneacetal structure ascribed to the product.

EXAMPLE XVI The process and procedure cited in Example XV was repeatedexactly, except that trans 1,2 dichloroethene was used in the place ofthe cis-1,2-dichliroethene. The observed exotherm was from 140 C. to 178C., and the sodium chloride yield was 73 g. (62.4% based on the sodium).Distillation of the liquid filtrate gave 78 grams of ketenedi(Z-methoxyethyl) acetal (44.4% yield) as the higher boiling fraction.The boiling point observed was 8082 C. at 1.8 millimeters of mercury.

The infrared spectrum of the ketene actal of this Example was identicalin all respects to infrared spectrum of the ketene acetal of Example XV.

EXAMPLE XVII The process and procedure cited in Example XV was repeatedexactly, except that vinylidene chloride was used in the place of thecis-1,2-dichlroethene (of Example XV). The observed exotherm was from140 to 173 C., and the sodium chloride yield was 68 g. (58.1% based onthe sodium). Distillation of the liquid filtrate and ether washings gave67 grams of ketene di(Z-methoxyethyl) acetal (38.1% yield) as the higherboiling fraction. The boiling point observed was 80-81 C. at 1.8millimeters of mercury.

The infrared spectrum of the ketene acetal of this Example was identicalin all respects to the infrared spectrum of the ketene acetal of ExampleXV.

EXAMPLE XVIII The process and procedure cited in Example XV was repeatedexactly, except that a stoichiometric excess of 1.24 moles ofcis-1,2-dichloroethene (120 grams) was used. The cis-1,2-dichloroethenewas fed over a 55 minute time period. The observed exotherm was from 135C. to 172 C., and the sodium chloride yield was quantitative at 119grams. Distillation of the liquid filtrate gave 111 grams of ketenedi(2methoxyethyl) acetal (63.1%

yield) as the major product fraction boiling at 83" C. at 1.7millimeters of mercury.

The infrared spectrum of the ketene acetal of this Example was identicalin all respects to the infrared spectrum of the ketene acetal of ExampleXV.

In addition to the major product fraction, described above, there was aminor fraction of 11 grams of 2- methoxyethyl orthoacetate having aboiling point of 112- 113 C. at 1.5 millimeters of mercury. The infraredspectra of this product was very different from the ketene acetaldescribed above, and shows a weak C C absorption at 1640 cm. togetherwith a weak 0 0 absorption at 1720 cmf The analysis of this productfraction was as follows:

Analysis.Calculated for C H O C, 52.4; H, 9.54. Found: C, 52.52; H,9.18. Molecular weight: Calculated 252. Found: 254 (Menzies-Wright inbenzene).

EXAMPLE XIX The process and procedure cited in Example XV was repeatedexactly, except that a stoichiometric excess of 1.24 moles oftrans-1,2-dichloroethene grams) was used. The trans-1,2-dichloroethenewas fed over a 34 minute time period. The observed exotherm was from C.to C. and the sodium chloride yield was 109 grams (93.1% based on thesodium). Distillation of the liquid filtrate and the ether washings gave103 grams of ketene di(2-methoxyethyl) acetal (58.5% yield as the higherboiling fraction boiling at 8082 C. at 1.8 millimeters of mercury.

The infrared spectrum of the ketene acetal of this Example was identicalin all respects to the infrared spectrum of the ketene acetal of ExampleXV.

EXAMPLE XX The process and procedure cited in Example XV was repeatedexactly, except that a stoichiometric excess of 1.24 moles of vinylidenechloride (120 grams) was used. The vinylidene chloride was fed over a 40minute time period. The observed exotherm was from 150 C. to 176 C., andthe sodium chloride yield was quantitative at 120 grams. Distillation ofthe liquid filtrate gave 133 grams of ketene di(Z-methoxyethyl) acetal(75.6% yield) as the higher boiling fraction boiling at 8183 C. at 1.9millimeters of mercury.

The infrared spectrum of the ketene acetal of this Example was identicalin all respects to the infrared spectrum of the ketene acetal of ExampleXV.

EXAMPLE XXI The process and procedure cited in Example XV was repeatedexactly, except that a stoichiometric excess of 1.24 moles of vinylidenechloride (120 grams) was used. In addition to this 50 grams of exlenewas used as the solvent in place of the diethylene glycol dimethyl etherof Example XV. The vinylidene chloride was fed over a 14 minute timeperiod, and the observed exotherm was from 140 C. to 174 C. The sodiumchloride yield was 114 grams (97.4% based on the sodium). Distillationof the combined liquid filtrate and ether washings gave 132 grams ofketene di(Z-methoxyethyl) acetal (75.0% yield) as the higher boilingproduct fraction boiling at 83 86 C. at 2.2 millimeters of mercury.

The infrared spectrum of the ketene acetal of this example was identicalin all respects to the infrared spectrum of the ketene acetal of ExampleXV.

EXAMPLE XXII The process and procedure cited in Example XX was repeatedexcept 1.25 moles of 1,2-di'bromoethene (232 grams) was used in place ofvinylidene chloride. The 1,2- dibromoethene was fed over a 26 minutetime period, and the observed exotherm was from 135 C. to 157 C. Thesodium bromide yield was 204 grams (99% based on the sodium).Distillation of the combined liquid filtrate and ether washings gave 66grams of tri-(2-methoxy- EXAMPLE XXIII The process and procedure citedin Example XV was repeated using 0.417 mole of 1,3-dimethoxy-2-pro anol(50.0 grams), 0.417 mole of metallic sodium (9.5 grams) and grams ofxylene. .261v mole of cis-1,2-dichloroethene (25.3 grams) was fed over a10-minute period, and the observed exotherm was from 140 C. to 157 C.The sodium chloride yield was 22 grams (91% based on the sodium).Distillation of the combined liquid filtrate and ether washings gave 20grams of di(1,3-dimethoxy-2- propyl) ketene acetal (36.4% yield) as thehigher boiling fraction boiling at 121-122 C. at 1.8 millimeters ofmercury.

Analysis.-Calculated for C H O C, 54.5; H, 9.09. Found: C, 54.5; H, 915.Molecular weight: Calculated 264. Found: 277 (Menzies-Wright inbenzene).

The infrared spectrum showed strong C=C absorption at 1650 cmf EXAMPLEXXIV The process and procedure cited in Example XV was repeated using2.0 moles of 2-methoxyethano1 (152 grams) 2.0 moles of sodium metal (46grams) and 50 grams of xylene, 1.25 moles of 1,1,2-trichloroethene(164.5 grams) were fed to the mixture over a 38 minute time period, andthe observed exotherm was from 137 C. to 150 C. The sodium chlorideyield was 108 grams (92% based on the sodium). Distillation of thecombined liquid filtrate and ether washings gave 112 grams of di(2-methoxyethyl) chloroketene acetal (53.2%yield) as the higher boilingproduct fraction boiling at 103 -106 C. at 1.6 millimeters of mercury.

Analysis.-Calculated for C H O Cl: C, 45.6; H, 7.12; Cl, 16.9. Found: C,46.0; H, 7.51; Cl, 17.3. Molecular weight: Calculated 210.5. Found: 211(Menzies-Wright in benzene).

The infrared spectrum showed strong C=C absorption at 1650 CHIS-1.

EXAMPLE XXV The process and procedure cited in Example XV was repeatedusing 2.0 moles of tetrahydropyran-Z-methanol (232 grams), 2.0 moles ofmetallic sodium (46.0 grams) and SO grams of xylene. 1.24 moles oftrans-1,2-dichloroethene (120 grams) was fed over a 37 minute timeperiod, and the observed exotherm was from 140 C. to 170 C. The sodiumchloride yield was quantitative at 120 grams. Distillation of thecombined .liquidfiltrate and ether washings gave 155 grams ofdi(tetrahydropyran-2- methyl) ketene acetal as the higher boilingproduct fraction (60.5% yield) boiling at 142145 C. at 1.5 millimetersof mercury.

Analysis.Calculated for C H O (256): C, 65.6; H, 9.38. Found: C, 65.8;H, 9.26. Molecular weight: Calculated 256. Found 274 (Menzies-Wright inbenzene).

A very strong C=C doublet appeared at 1640 and 1660 cm.-

EXAMPLE XXVI The process and procedure cited in Example XV was repeatedusing 1.0 mole of 2,2-dimethyl-1,3-dioxolane-4- methanol (107 grams),1.0 mole of metallic sodium (23 grams), and 50 grams of diethyleneglycol dimethyl ether as the inert solvent. 0.62 mole oftrans-1,2-dichloroethene (60 grams) was fed to the mixture over a 14minute period, and the observed exotherm was from 130 C. to 158 C. Thesodium chloride yield was quantitative at 66 grams (based on thesodium). Distillation of the combined liquid filtrate and ether washingsgave 44 grams of di(2,2-dimethyl 1,3 dioxolane-4-methyl) ketene acetal(0.153 mole) (30.6% yield) as the higher boiling product fraction.Cooling of this product to room temperature, or below, resulted in theformation of colorless matted needles. The product had a boiling pointof 130 132 C. at 1.1 millimeters of mercury, and a melting point of 2730 C.

Analysis.Calculated for C H O (288): C, 58.3; -H, 8.39. Found: C, 57.9;H, 8.60. Molecular weight: Calculated 288. Found: 288 (Menzies-Wright inbenzene).

The infrared spectrum showed strong C=C absorption at 1640 cmf EXAMPLEXXVII The process and procedure cited in Example XV was repeated using2.0 moles of 2-methoxyethanol (152 grams) 2.0 moles of metallic sodium(46.0 grams) and 50 grams of xylene. 1.25 moles of1,2,3-trichloro-1-propene (182 grams) was fed to the mixture over a 41minute time period, and the observed exotherm was from 135 C. to 153 C.The sodium chloride yield was quantitative at 120 grams. Distillation ofthe combined liquid filtrate and ether washings gave 23 grams of acolorless liquid as the higher boiling product fraction. This fractionobtained was redistilled and the major fraction obtained from theredistillation, said fraction boiling at 110.5 C. at 1.5 millimeters ofmercury was analyzed.

Analysis.Calculated for C H O Cl: C, 48.1; H, 7.63; CI, 15.78. Found: C,49.81; H, 6.80; CI, 8.66.

EXAMPLE XXVIII To a flask equipped with a stirrer and condenser areadded 1.0 mole of B-methoxy-Lpropanol (90.0 grams) and 100 grams ofdiethylene glycol dimethyl ether. 1.0 mole of metallic sodium (23.0grams) was dissolved therein over a 2 hour period at a temperature of-440 C.

To the mixture was added dropwise 0.62 mole of vinylidene chloride (60.0grams) over a 15 minute time period. The temperature of the flaskcontents rose from 130 C. to a maximum of 156 C., with the concomitantprecipitation of solid sodium chloride. Stirring was continued for anadditional 10 minute after the vinylidene chloride addition wascompleted. Diethyl ether (2.00 grams) was then added to the flask andthe mixture vacuum filtered through a tritted glass funnel. The vacuumdried sodium chloride yield was 50 grams (85% based on the sodium).

The liquid filtrate was vacuum distilled to yield, as the higher boilingproduct fraction, 16 grams of di(3-rnethoxy-l-propyl) ketene acetal(15.7% yield) which had a boiling point of 101 -102 C. at 2.8millimeters of mercury.

Andlysis.-Calculated for C H 0 C, 58.8; H, 9.81. Found: C, 58.95; H,9.97. Molecular weight: Calculated 204. Found: 203 (Menzies-Wright inbenzene).

The infrared spectrum showed strong C=C absorption at 1640 cmr EXAMPLEXXIX To a flask equipped with a stirrer and condenser are added 2.0moles of 3-methoxy-1-butanol (208 grams), and 50 grams of xylene. 2.0moles of metallic sodium (46.0 grams) was dissolved therein over a 2hour period at a temperature of 120-150 C. and 1.24 moles of vinylidenechloride (120 grams) was added dropwise over a 15 minute time period.The temperature of the flask contents rose from C. to a maximum of 154C. Stirring was continued for an additional 10 minutes after theaddition was complete. Diethyl ether (100 milliliters) was then added tothe flask, serving to both cool the flask contents to about 60 C., andto reduce the viscosity. This mixture was then vacuum filtered through afritted glass funnel. The solid sodium chloride cake was Washed with3-20 milliliter portions of fresh diethyl ether. The vacuum dried solidsodium chloride yield was 93 grams (79% based on the sodium).

The combined liquid filtrate and ether washings were 19 vacuum distilledto yield, as the higher boiling fraction, 83 grams of ketenedi(3-methoxy-1-butyl) acetal (35.8% yield) which had a boiling point of100-l04 C. at 1.5 millimeters of mercury.

Analysis.Calculated for C H O C, 62.1; H, 10.35. Found: C, 62.3; H,10.67. Molecular weight: Calculated 232. Found: 237(MenZies-Wright inbenzene).

The infrared spectrum showed strong C=C absorption at 1640 cmf EXAMPLEXXX The process and procedure cited in Example XXIX was repeatedexactly, except that a stoichiometric excess of 1.24 moles ofcis-1,2-dichloroethene (120 grams) was used. The cis-1,2-dichloroethenewas fed over a 17 minute time period. The observed exotherm was from 141C. to 156 C., and the sodium chloride yield was quantitative at 132grams. Distillation of the combined liquid filtrate and ether washingsgave 87 grams of ketene di(3-methoxy-1-butyl) acetal (37.5% yield) asthe major product fraction boiling at 104105 C. at 1.6 millimeters ofmercury.

The infrared spectrum of the ketene acetal of this Example was identicalin all respects to the infrared spectrum of the ketene acetal of ExampleXXIX.

EXAMPLE XXXI To a flask was added 0.00142 mole of ketene di(2-methoxyethyl) acetal (2.50 grams) and 0.001 gram of anhydrous calciumchloride. The flask was stoppered and maintained at room temperature for24 hours. There was formed an essentially quantitative yield of thehomopolymer of ketene di(Z-methoxyethyl) acetal which appeared as awhite solid and exhibited a melting point of 198208 C. The polymerdarkened upon heating. The white solid was then vacuum dried at 60 C.for 18 hours and 23 millimeters of mercury to give a light brown solidmelting at 200 to 210 C. analyzed as follows:

Analysis.Calculated for OC2H5OCH2/u C, 54.5; H, 9.16. Found: C, 54.34;H, 9.62.

EXAMPLE XXXII The process and procedure of Example 31 was repeated with0.00198 mole of ketene di(3,4-dihydro-2H-pyran-2- methyl) acetal (5.00grams) and 0.001 gram of anhydrous calcium chloride. These materialswere maintained at 60 C. for 24 hours and yielded a waxy yellowpolymeric product identified as the homopolymer of the di(3,4-dihydro-2H-pyran-2-methyl) acetal. After vacuum drying the weightloss was 0.05 gram indicating a quantitative yield of homopolymer.Analysis of the polymer was as follows: C, 65.34, H, 8.25.

EXAMPLE XXXIII In a stoppered bottle were placed 0.050 mole of ketenedi(Z-methoxyethyl) acetal (8.80 grams), 0.050 mole of ethyl vinyl ether,(3.60 grams) and 0.002 gram of anhydrous calcium chloride. The contentswere maintained overnight at room temperature. There was obtained asolid mass of a colorless waxy solid which was vacuum dried at 100 C.and 1-2 millimeters of mercury for 1 hour to yield 1.20 grams of ayellow solid copolymer of ketene di(2-methoxyethyl) acetal and ethylvinyl ether equivalent to a 67% yield. The copolymer was a tackywax-like solid which was water soluble and was analyzed as follows: C,52.48; H, 8.68.

EXAMPLE XXXIV l-bromo-2-ethoxyethene was prepared by the reaction ofvinyl ethyl ether and bromine in the presence of a N,N-

20 dimethylanaline in a light petroleum ether solvent at 40 C.

To a solution of 0.50 mole of Z-methoxyethanol (380 grams) in 25 gramsof xylene was added 11.5 grams of methyl sodium at a temperature of -130C. under a nitrogen atmosphere. When solution of sodium was complete,l-bromo-Z-ethoxyethene prepared above was added dropwise to the mixtureover a 50-minute period at -140 C. with rapid stirring. Stirring wascontinued for an additional two hours at C. with the precipitation ofsolid sodium bromide. The reaction mixture was then filtered to yield ayellow liquid filtrate and the solid sodium bromide. The sodium bromidewas washed several times with anhydrous ether and was dried overnight.The yield was 39 grams which was equivalent to a 76% yield based uponthe sodium used in the reaction. Distillation of the combined liquidfiltrates and ether washings gave 35 grams of ketene ethyl2-methoxyethyl acetal (48.0% yield) as the principle product fraction.The product had a boiling point of 40.0-40.5 C. at 0.5 millimeter ofmercury. The analysis was as follows:

Analysis.Calculated for CqHmOgI C, 57.5; H, 9.65. Found: C, 57.3; H,9.89. Molecular weight: Calculated 146. Found: 148 (Menzies-Wright inbenzene).

The infrared spectrum showed a strong C=C absorption at 1640 cm.

What is claimed is:

1. A ketene acetal of the formula:

0-alkylene-OR wherein R is alkylidene containing from 1 to 4 carbonatoms and R and R are alkyl containing from 1 to 6 carbon atoms and saidalkylene group is selected from the class consisting of 1,2- and1,3-alkylene groups.

2. Ketene di(Z-methoxyethyl) acetal.

3. Ketene di(2-(N,N-dimethylaminoethyl)) acetal. 4. A compound of theformula:

(1) where n is an integer from 2 to 3, and m is an integer from 0 to 1;

(2) wherein A represents an organic radical selected from the groupconsisting of tertiary alkyl radicals of the formula:

and secondary l-alkenyl radicals of the formula:

wherein R is selected from the group consisting of alkyl andchloroalkyl, each containing from 1 to 4 carbon atoms, and R is selectedfrom the group consisting of alkylidene and chloroalkylidene, eachcontaining from 1 to 4 carbon atoms;

(3) wherein X is selected from the group consisting of O-, and

wherein R" is alkyl, of from 1 to 4 carbon atoms;

(4) wherein each R individually is selected from the group consisting ofhydrogen, alkyl of from 1 to 8 carbon atoms and monocyclic and bicyclichydrocarbon aryl, alkaryl and aralkyl groups contain- 6 to 12 carbonatoms, and when taken with R forms R forms part of a saturated divalentchain which forms a heterocyclic ring containing X as the heterocyclicatom;

(5) wherein R is selected from the group consisting of alkyl of from 1to 6 carbon atoms, alkoxyalkyl and polyoxyalkylene, containing 2 to 4carbonatoms ineach alkylene unit, and when taken with any R forms partof a saturated divalent chain which forms a heterocyclic ring containingX as the heterocyclic atom.

5. A ketene acetal of the formula:

Reclolifililam) 1211121,,

(1) wherein m is an integer from to 1;

' (2) wherein R is selected from the group consisting of alkylidene andchloroalkylidene, each containing from 1 to 4 carbon atoms;

(3) wherein X is selected from the group consisting of O, and

wherein R" is alkyl of from 1 to 4 carbon atoms;

(4) wherein each R individually is selected from the group consisting ofhydrogen, alkyl of from 1 to 8 carbon atoms and monocyclic and bicyclichydrocarbon aryl, alkaryl and aralkyl groups containing 6 to 12 carbonatoms, and when taken with R forms part of a saturated divalent chainwhich forms a heterocyclic ring containing X as the heterocyclic atom;

(5) wherein R is selected from the group consisting of alkyl of from 1to 6 carbon atoms, alkoxyalkyl and polyoxyalkylene each containing 2 to4 carbon atoms in each alkylene unit, and when taken with any R formspart of a saturated divalent chain which forms a heterocyclic ringcontaining X as the heterocyclic atom.

6. An orthoester of the formula:

2 2 R2 mlaatitlm) M11 1 (1) wherein m is an integer from 0 to l;

(2) wherein R is selected from the group consisting of alkyl andchloroalkyl, each containing from 1 to 4 carbon atoms;

(3) wherein X is selected from the group consisting of O-, and

I'll! (N-) wherein R" is alkyl, of from 1 to 4 carbon atoms;

(4) wherein each R individually is selected from the group consisting ofhydrogen, alkyl of from 1 to 8 carbon atoms and monocyclic and bicyclichy-drocarbon aryl, alkaryl and aralkyl groups containing 6 to 12 carbonatoms, and when taken with R forms part of a saturated divalent chainwhich forms a heterocyclic ring containing X as the heterocyclic atom;

(5) wherein R is selected from the group consisting of alkyl of from 1to 6 carbon atoms, alkoxyalkyl, and polyoxyalkylene each containing 2 to4 carbon atoms in each alkylene unit, and when taken with any R formspart of a saturated divalent chain which forms a heterocyclic ringcontaining X as the hetero cyclic ring containing X as the heterocyclicatom.

7. A process for the production of ketene metals which comprisesreacting (a) sodium alcoholates of alcoholic hydroxy compounds of theformula:

wherein m is an integer from 0 to 1, wherein X is selected from thegroup of O-, and

wherein R" is alkyl of from 1 to 4 carbon atoms, wherein each Rindividually is selected from the group consisting of hydrogen, alkyl of'from 1 to 8 carbon atoms and monocyclic and bicyclic hydrocarbon aryl,alkaryl and aralkyl groups containing 6 to 12 carbon atoms, and whentaken with R forms part of a divalent saturated chain which forms aheterocyclic ring containing X as the heterocyclic atom, and wherein Ris selected from the group consisting of alkyl of from 1 to 6 carbonatoms, alkoxyalkyl and polyoxyalkylene containing 2 to 4 carbon atoms ineach alkylene unit, and when taken with any R forms part of a divalentsaturated chain which forms a heterocycle containing X as theheterocyclic atom; with (b) a haloalkene of the formula:

wherein Y is selected from the group consisting of halogen and hydrogen,at least two of said Y moieties being halogen, and wherein R is selectedfrom the class of hydrogen and alkyl with the proviso that if R is alkylat least one Y moiety is hydrogen; in such amount as to provideapproximately two moles of said alcoholate per mole of saiddihaloalkene.

8. The process of claim 7 wherein the haloalkene is a dichloroethene.

9. A process for the production of orthoesters which comprises reactinga solution comprising (a) an alcoholic hydroxy compound and a compoundselected from the group of sodium alcoholates of an alcoholic hydroxycompound, wherein said alcoholic hydroxy compound corresponds to theformula:

wherein m is an integer from 0 to 1, wherein X is selected from thegroup of O--, and

wherein R is alkyl, of from 1 to 4 carbon atoms, wherein each Rindividually is selected from the group consisting of hydrogen, alkyl offrom 1 to 8 carbon atoms and monocyclic and bicyclic hydrocarbon aryl,alkaryl and aralkyl groups containing 6 to 12 carbon atoms, and whentaken with R forms part of a divalent saturated chain which forms aheterocyclic ring containing X as the heterocyclic atom, and wherein Ris selected from the group of alkyl of from 1 to 6 carbon atoms,alkoxyalkyl and polyoxyalkylene containing 2 to 4 carbon atoms in eachalkylene unit, and when taken with any R forms part of a divalentsaturated chain which forms a heterocycle containing X as theheterocyclic atom; with (b) a haloalkene of the formula:

wherein Y is selected from the group consisting of halogen and hydrogen,at least two of said Y moieties being halogen, and wherein R is selectedfrom the class of hydrogen ,alkyl with the proviso that if R is alkyl atleast one Y moiety is hydrogen; the said. alcoholate being present in anamount so as to provide at least two moles of the said alcoholate permole of the said dichloroalkene, the said alcoholic hydroxy compoundbeing present in both the alcoholate and the hydroxy form in an amountso as to provide at least 3 moles of the 23 said alcoholic hydroxycompounds per mole of the said dichloroalkene.

10. A process for producing mixed ketene acetals which comprisesreacting (a) a compound selected from the group consisting of sodiumalcoholates of alcoholic hydroxy compounds of the formula:

wherein m is an integer from 0 to 1, wherein X is selected from thegroup of O, and

RI! ML) wherein R" is alkyl of from 1 to 4 carbon atoms, wherein each Rindividually is selected from the group consisting of hydrogen, alkyl offrom 1 to 8 carbon atoms and monocyclic and bicyclic hydrocarbon aryl,alkaryl and aralkyl groups containing 6 to 12 carbon atoms, and whentaken with R forms part of a divalent saturated chain which forms aheterocyclic ring containing X as the heterocyclic atom, and wherein Ris selected from the group consisting of alkyl of from 1 to 6 carbonatoms, alkoxyalkyl and polyoxyalkylene containing 2 to 4 carbon atoms ineach alkylene unit, and when taken with any R forms part of a divalentsaturated chain which torms a heterocycle containing X as theheterocyclic atom; with (b) a fi-halo-a,fi-alkenyl ether of the formula:

No references cited.

NICHOLAS S. RIZZO, Primary Examiner.

F. A. MIKA, Assistan Examiner.

US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,419,580 December 31, 1968 William C. Kuryla It is certified that errorappears in the above identified patent and that said Letters Patent arehereby corrected as shown below:

In the heading to the printed specification, line 2,

"KETONE" should read KETENE Column 1, lines 41 to 43, the formula shouldappear as shown below:

Column 2, lines 45 to 47, the formula should read as shown below R-C|5Oalkylene-)- 0-R 3 Column 4, line 11, the formula should appear asshown below:

(9 R-O-CH CH ONa Column 5, lines 48 to 51, the formula should appear asshown below:

Column 7, lines 25 to 29, that portion of the formula reading readColumn 19, lines 40 to 43, the formula should appear as shown Signed andsealed this 24th day of March 1970.

below:

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Attesting Officer

4. A COMPOUND OF THE FORMULA: